US20080308765A1

US20080308765A1 - Process for Preparing Vinyl Carboxylates

Info

Publication number: US20080308765A1
Application number: US12/092,222
Authority: US
Inventors: Wolfgang Staffel; Roland Kessinger; Jochem Henkelmann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-11-23
Filing date: 2006-11-22
Publication date: 2008-12-18
Also published as: JP5145237B2; US8044233B2; JP2009516723A; WO2007060176A1; KR20080069701A; EP1954666A1; KR101374505B1

Abstract

The present invention relates to a process for preparing vinyl carboxylates, wherein a carboxylic acid is reacted with an alkyne compound in the presence of a catalyst which is selected from carbonyl complexes, halides and oxides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron and rhenium metal at a temperature of ≦300° C.

The process gives the desired vinyl esters with high yield.

Description

The present invention relates to a process for preparing vinyl carboxylates by reacting a carboxylic acid with an alkyne.
The addition of carboxylic acids to alkynes to prepare the corresponding vinyl carboxylates has been known for some time. Suitable catalysts used are especially zinc salts, such as the zinc salt of the carboxylic acid taking part in the reaction; see, for example, U.S. Pat. No. 2,066,075, U.S. Pat. No. 3,455,998 and U.S. Pat. No. 3,607,915.
Since the zinc salts have only low selectivity and stability, attempts have been made to use other catalysts. For instance, U.S. Pat. No. 5,430,179 describes the use of ruthenium complexes soluble in the reaction medium with a phosphine ligand. EP 512 656 A describes a process for preparing vinyl derivatives of Brønsted acids, such as carboxylic acids, by reacting the Brønsted acid with an acetylenically unsaturated compound in the presence of a ruthenium catalyst which is applied to an inter porous support. J. Org. Chem. 2004, 69, 5782-5784 describes the reaction of terminal alkynes with acetic acid or benzoic acid using Re(CO)₅Br as the catalyst. It has been found that the anti-Markovnikov adduct is obtained with high selectivity especially in n-heptane and toluene as solvents. Organometallics 2000, 19, 170-183 describes the intramolecular hydroamination of aminoalkyne compounds using [Re(CO)₅(H₂O)]BF4 as a catalyst. However, only a low yield is obtained.
It is common to the prior art process that the yield of vinyl esters is not satisfactory.
It is therefore an object of the present invention to provide a process for preparing vinyl carboxylates which proceeds with high yield.
Moreover, the process shall be performable at temperatures at which even the thermally labile carboxylic acids and vinyl carboxylates do not decompose.
Finally, the process shall be performable with small amounts of catalyst in order to restrict the costs for the catalyst.
It has now been found that, surprisingly, this object is achieved when the catalyst used is a carbonyl complex, a halide or oxide of rhenium, of manganese, of tungsten, of molybdenum, of chromium, of iron or rhenium metal.
The present invention therefore provides a process for preparing vinyl carboxylates of the formula I:
in which

a) R¹is H or —COO—CH═CH—R²and n is 1, or
b) R¹is C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₃-C₇-cycloalkyl, and n is 1, 2, 3 or 4, where R¹is optionally substituted by 1, 2 or 3 radicals which are each independently selected from phenyl, halogen, hydroxy, C₁-C₄-alkoxy, amino, mono-C₁-C₄-alkyl-amino, di-C₁-C₄-alkylamino, —OCOR³, —COOR³, —CONR⁴, R⁵, —NR⁴COR⁵, —OCONR⁴R⁵or —NR⁴COOR⁵, or
c) R¹is aryl and n is 1, 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from C₁-C₄-alkyl, halogen, hydroxy C₁-C₄-alkoxy, amino, mono-C₁-C₄-alkylamino, di-C₁-C₄-alkylamino, —OCOR³, —COOR³, —CONR⁴R⁵, —NR⁴COR⁵, —OCONR⁴R⁵or —NR⁴COOR⁵, or
d) R¹is bicycloalkyl having from 6 to 9 or from 7 to 9 carbon atoms or bicycloalkenyl having from 6 to 9 or from 7 to 9 carbon atoms and one or two carbon-carbon double bonds, and n is 1 or 2, where the bicycloalkyl radical may be substituted by 1, 2, 3, 4, 5 or 6 radicals which are each independently selected from halogen or C₁-C₄-alkyl, or
e) R¹is five- or six-membered heterocyclyl which has one or two heteroatoms which are each independently selected from N, O and S, and n is 1, 2 or 3, where the heterocyclyl radical may be substituted by 1 or 2 radicals which are each independently selected from halogen or C₁-C₄-alkyl;
R²is H, C₁-C₈-alkyl, phenyl-C₁-C₄-alkyl, phenyl which is optionally substituted by 1 or 2 C₁-C₄-alkyl groups, or C₃-C₇-cycloalkyl;
R³is C₁-C₄-alkyl;
R⁴and R⁵, which may be the same or different, are each H or C₁-C₄-alkyl; comprising the reaction of a compound of the formula II

in which R¹is H, —COOH or as defined above under b) or c) and n is as defined above with a compound of the formula III
H—C≡C—R² (III)
in which R²is as defined above, in the presence of a catalyst which is selected from carbonyl complexes, oxides and halides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron and rhenium metal at a temperature of ≦300° C.
A preferred embodiment of the present invention is a process for preparing vinyl carboxylate compounds of the formula I:
in which

a) R¹is H or —COO—CH═CH—R²and n is 1,
b) R¹is C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₃-C₇-cycloalkyl, and n is 1, 2, 3 or 4, in particular 1, 2 or 3, where R¹is optionally substituted by 1 or 2 radicals which are each independently selected from phenyl, halogen, hydroxy, C₁-C₄-alkoxy, amino, mono-C₁-C₄-alkylamino, di-C₁-C₄-Alkylamino, —OCOR³, —COOR³, —CONR⁴R⁵, —NR⁴COR⁵, —OCONR⁴R⁵or —NR⁴COOR⁵, or
c) R¹is aryl and n is 1, 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from C₁-C₄-alkyl, halogen, hydroxy C₁-C₄-alkoxy, amino, mono-C₁-C₄-alkylamino, di-C₁-C₄-alkylamino, —OCOR³, —COOR³, —CONR⁴R⁵, —NR⁴COR⁵, —OCONR⁴R⁵or —NR⁴COOR⁵, or
R²is H, C₁-C₈-alkyl, phenyl-C₁-C₄-alkyl, phenyl which is optionally substituted by 1 or 2 C₁-C₄-alkyl groups, or C₃-C₇-cycloalkyl;
R³is C₁-C₄-alkyl;
R⁴and R⁵, which may be the same or different, are each H or C₁-C₄-alkyl;
comprising the reaction of a compound of the formula II

in which R¹is H, —COOH or as defined above under b) or c) and n is as defined above with a compound of the formula III
H—C≡C—R² (III)
in which R²is as defined above, in the presence of a catalyst which is selected from carbonyl complexes, oxides and halides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron at a temperature of ≦300° C., preferably ≦260° C., in particular ≦230° C.
In a further preferred embodiment, the invention relates to a process for preparing vinyl carboxylate compounds of the formula I:
in which

a) R¹is H or —COO—CH═CH—R²and n is 1,
b) R¹is C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₃-C₇-cycloalkyl, and n is 1, 2, 3 or 4, in particular 1, 2 or 3, where R¹is optionally substituted by 1 or 2 radicals which are each independently selected from phenyl, halogen and C₁-C₄-alkoxy or
c) R¹is aryl and n is 1, 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from C₁-C₄-alkyl, halogen and C₁-C₄-alkoxy;
R²is H, C₁-C₈-alkyl, phenyl-C₁-C₄-alkyl, phenyl which is optionally substituted by 1 or 2 C₁-C₄-alkyl groups, or C₃-C₇-cycloalkyl;
by reacting a compound of the formula II

in which R¹is H, —COOH or as defined above under b) or c) and n is as defined above with a compound of the formula III
H—C≡C—R² (III)
in which R²is as defined above, in the presence of a catalyst which is selected from carbonyl complexes of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron at a temperature of ≦300° C., preferably ≦260° C., in particular ≦230° C.
The alkyl groups may be straight-chain or branched alkyl groups having the carbon number specified. Examples of such alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-hexyl, n-dodecyl, etc.
Examples of C₂-C₂₀-alkenyl groups are vinyl, 1- or 2-propenyl, buten-1-yl, buten-2-yl and isobutenyl.
Halogen means fluorine, chlorine, bromine or iodine.
Examples of C₃-C₇-cycloalkyl groups are cyclopropyl, cyclobutyl, cycloheptyl and especially cyclopentyl and cyclohexyl.
Examples of bicycloalkyl groups are bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane and bicyclo[2.3.2]nonane.
Examples of bicycloalkenyl groups are bicyclo[2.2.1]heptene, bicyclo[2.2.2]octene and bicyclo[2.3.2]nonene.
Heterocyclyl may be aromatic or saturated or unsaturated nonaromatic heterocyclyl.
Examples of aromatic heterocyclyl are pyridyl, pyrimidyl, triazinyl, pyrrolyl, furyl, thienyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, thiadiazolyl or triazyl. Examples of saturated heterocyclyl are pyrrolidinyl, tetrahydro-furanyl, piperidinyl, morpholinyl or piperazinyl.
Aryl means preferably phenyl or naphthyl.
When R¹has the above-specified definition b), n is preferably 1 or 2. When R¹has the above-specified definition c), n is preferably 1, 2 or 3.
The catalyst used comprises the carbonyl complexes, oxides or halides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron. Carbonyl complexes are understood here to mean compounds which have at least one carbonyl group as a ligand. The remaining coordination sites can be occupied by other ligands as listed by way of example in the paragraph below. Oxides and halides are also understood to mean compounds in which one or more coordination sites and/or valences are occupied by a C₁-C₈-alkyl group, and also oxyhalides. Examples thereof are CH₃ReO₃, ReO₃Cl, or ReOCl₄.
The catalysts may be present in all oxidation states; in the case of carbonyl complexes, they are preferably present in the 0 or I oxidation state. Preferred catalysts are the carbonyl complexes, oxides or halides of rhenium, of manganese or of molybdenum and especially of rhenium, the carbonyl complexes of rhenium or of manganese having been found to be particularly suitable.
Particularly effective carbonyl complexes are those of the abovementioned metals. One or more of the carbonyl groups may be replaced by suitable ligands such as H₂O, halogens, especially chlorine or bromine, phosphine ligands such as triphenylphosphine, trimethylphosphine, triethylphosphine, tri-n-butylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinobutane, diphenylphosphinoferrocene, etc., amine ligands such as NH₃, ethylenediamine, etc., alcohol ligands such as phenol, methanol, ethanol, etc., thio ligands such as methyl mercaptan or thiophenol. Examples of suitable carbonyl complex catalysts are Mn₂(CO)₁₀, Fe(CO)₅, Fe₂(CO)₉, Mo(CO)₆, W(CO)₆and Cr(CO)₆.
Particularly suitable catalysts have been found to be the rhenium catalysts. Examples thereof are Re₂(CO)₁₀, Re(CO)₅Cl, Re(CO)₅Br, ReBr(CO)₃(CH₃CN)₂, ReCp(CO)₃, Re(pentamethyl-Cp)(CO)₃, ReCl(CO)₃(CH₃CN)₂, ReBr(CO)₃(THF)₂, ReCp₂, ReCl(CO)₃(THF)₂, Re₂(pentamethyl-Cp)₂(CO)₃, Re₂(pentamethyl-Cp)₂O₄, Re(pentamethyl-Cp)OCl₂(Cp=cyclopentadiene; THF=tetrahydrofuran), Re₂O₇, Re, ReCl₃, ReBr₃and ReCH₃O₃. A particularly preferred catalyst is Re₂(CO)₁₀.
The reaction can be effected in homogeneous or heterogeneous liquid phase. When a homogeneous liquid phase is desired, a catalyst is used which is soluble in the reaction medium under the given reaction conditions or goes into solution during the reaction. Such catalysts are in particular the carbonyl complexes of the metals which are useful here. Heterogeneous catalysts are the halides and oxides of these metals, and rhenium metal. The heterogeneous catalysts can be used directly, for example in powder form, or applied to a support. Suitable supports are carbon powder, zeolites, aluminum oxides silicon oxides, etc.
In general, the catalyst is used in an amount of from 0.000005 to 1 mol %, preferably from 0.000005 to 0.5 mol %, more preferably from 0.00001 to 0.1 mol % and in particular from 0.00005 to 0.05 mol %, from 0.0001 to 0.05 mol %, from 0.0005 to 0.01 mol % or from 0.001 to 0.01 mol %, based in each case on equivalents of the compound of the formula II. The expression “equivalents” relates here to carboxyl groups of the formula II which can react with the compound of the formula III.
Suitable starting compounds of the formula II are aliphatic monocarboxylic acids. Examples of such carboxylic acids are formic acid, acetic acid, halogenated carboxylic acids, such as chloroacetic acid or trifluoroacetic acid, propionic acid, aminocarboxylic acids, such as alanine, lactic acid or butyric acid, hydroxycarboxylic acids, such as hydroxybutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-methylpropionic acid, 2-methylbutyric acid, 3-methylbutyric acid, 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, tertiary carboxylic acids of the formula R⁶R⁷C(CH₃)COOH in which R⁶and R⁷are each independently C₁-C₁₂-alkyl, such as pivalic acid, 2,2-dimethylbutyric acid, 2,2-dimethylpentanoic acid, 2,2-dimethylhexanoic acid, 2,2-dimethylheptanoic acid, 2,2-dimethyloctanoic acid (Versatic acids 6, 7, 8, 9, 10), neononanoic acid, neodecanoic acid, neotridecanoic acid, stearic acid, oleic acid, lauric acid, palmitic acid, cyclohexanemono- and cyclohexanepolycarboxylic acids such as cyclohexane-carboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid or phenylacetic acid.
Suitable starting compounds of the formula II are also aliphatic polycarboxylic acids, especially dicarboxylic acids, and the derivatives of the polycarboxylic acids which have been partly esterified with a C₁-C₄-alkanol and partly amidated with ammonia, a C₁-C₄-monoalkylamine or a di-C₁-C₄-alkylamine. Examples of aliphatic polycarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, agaricic acid, 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, citric acid, malic acid, tartaric acid, glutamic acid, maleic acid and fumaric acid, particular preference being given to the use of adipic acid.
Suitable starting compounds of the formula II are also bicyclic mono- and dicarboxylic acids such as
Suitable starting compounds of the formula II are also heterocyclic mono- and polycarboxylic acids and the derivatives of the polycarboxylic acids which have been partly esterified with a C₁-C₄-alkanol and partly amidated with ammonia, a C₁-C₄-mono-alkylamine or a di-C₁-C₄-alkylamine. Examples thereof are 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid or 4-pyridinecarboxylic acid, pyridinedicarboxylic acids such as 2,3- and 2,4-pyridinedicarboxylic acid, furan-2-carboxylic acid, furan-3-carboxylic acid, thiophene-2-carboxylic acid, thiophene-3-carboxylic acid or proline.
Suitable starting compounds of the formula II are also aromatic monocarboxylic acids and polycarboxylic acids and the derivatives of the polycarboxylic acids which have been partly esterified with a C₁-C₄-alkanol and partly amidated with ammonia, a C₁-C₄-monoalkylamine or a di-C₁-C₄-alkylamine. Examples of such carboxylic acids are benzoic acid, 2-, 3- or 4-methylbenzoic acid, salicylic acid, 2-, 3- or 4-aminobenzoic acid, 4-dimethylaminobenzoic acid, phthalic acid, isophthalic acid or terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid, benzenepentacarboxylic acid and benzenehexacarboxylic acid, and the derivatives of the polycarboxylic acids which have been partly esterified with a C₁-C₄-alkanol.
The starting compounds of the formulae II and III are commercially available or preparable by known processes. The above-described bicyclic carboxylic acids are obtainable by Diels-Alder reaction of cyclopentadiene, cyclohexadiene or cycloheptadiene with acrylic acid, maleic acid or fumaric acid, and if appropriate hydrogenation to the saturated mono- and dicarboxylic acids.
Suitable starting compounds of the formula III are, for example, acetylene, propyne, 1-butyne, 1-pentyne, 1-hexyne and phenylacetylene, particular preference being given to using acetylene.
The quantitative ratio of compound of the formula II to compound of the formula III can be selected within a wide range. In general, though, an excess of compound of the formula III is used, especially an excess of from 0.1 to 20 mol %, based on the compound of the formula II.
The reaction is generally carried out in a suitable inert solvent. If the compound of the formula II is liquid at the temperature employed, it is possible to dispense with a solvent. Suitable inert solvents are aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, decalin, paraffin oil, toluene, xylene, etc., ethers such as tetrahydrofuran, dioxane or diphenyl ether, chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane or chlorobenzene, esters such as ethyl acetate, n-butyl acetate or butyrolactone, acetonitrile, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or polyethylene glycols or mixtures thereof. The reaction can also be performed in a compound of the formula I as a solvent if it is liquid at the selected reaction temperature.
The reaction temperature can be selected freely within a wide range. It is generally selected such that there is rapid conversion without starting compounds or the products decomposing. It is appropriately ≦300° C., preferably ≦260° C., more preferably ≦250° C. and in particular ≦230° C. In general, the temperature is in the range from 70 to 300° C., from 80 to 280° C., in particular from 100 to 260° C., from 100 to 250° C., from 100 to 230° C., from 100 to 210° C. or 110 to 200° C., preferably from 120 to 180° C., from 130 to 170° C., from 140 to 170° C. and especially from 150 to 170° C.
The reaction is typically carried out under pressure, preference being given to establishing from 1 to 30 bar (absolute), preferably from 2 to 20 bar and in particular from 5 to 25 bar or from 10 to 20 bar. The pressure may, for example, be established with the compound of the formula III employed and/or an inert gas such as nitrogen. The reaction time is generally in the range from 0.5 to 72 hours, especially from 1 to 48 hours.
If appropriate, it is also possible to add reaction-promoting additives such as zinc acetate, lithium salts, for example LiCl, Lewis acids such as BF₃, etc., Lewis bases such as triethylamine, pyridine, 1,5-diazabicyclo[4.3.0]non-5-ene, etc., substances which react with the catalyst on CO and can thus create free coordination sites, for example trimethylamino N-oxide.
The reaction can be carried out batchwise, continuously or in a semibatchwise process. The workup is effected in a customary manner, appropriately by distilling off the desired vinyl carboxylates. The catalyst remains in the bottoms and can be reused if appropriate. Appropriately, the reaction and the workup, especially the purifying distillation, can be carried out in the presence of a polymerization inhibitor. The polymerization inhibitors used may, for example, be hydroquinone, hydroquinone monomethyl ether, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, nitroso compounds such as isoacryloyl nitrate, nitrosodiphenylamine, N-nitrosocyclohexyl-hydroxyamine, methylene blue, phenothiazine, tannic acid or diphenylamine. The polymerization inhibitors are used generally in amounts of from 1 to 10 000 ppm, especially of from 100 to 1000 ppm, based in each case on the overall mixture.
The reaction proceeds selectively, i.e., even in the presence of other vinylatable groups in the compound of the formula II, such as OH or NH₂, only the carboxyl groups are vinylated. If a compound of the formula II is used which, as well as the carboxyl group(s), also comprises another vinylatable group, the reaction temperature is appropriately selected within the range from 70 to 160° C. and/or the reaction time within the range from 0.5 to 12 hours.
A preferred embodiment of the invention relates to the reaction of the compounds of the formula II in which R¹is H, C₁-C₆-alkyl, C₃-C₇-cycloalkyl or phenyl, where the alkyl group may be substituted as specified above under b) and the phenyl group as specified above under c), and n is 1 with acetylene.
A further preferred embodiment relates to the reaction of the compounds of the formula II in which R¹is CO₂H and n is 1, or in which R¹is C₁-C₂₀-alkyl, especially C₁-C₄-alkyl, where R¹may be substituted as specified under b) above, and n is 2, with acetylene. Preference is given to carrying out this reaction at a temperature in the range from 70 to 220° C., preferably from 130° C. to 220° C., in particular from 140 to 180° C. or from 150 to 170° C. Catalyst is used especially in an amount of from 0.00001 to 0.1 mol %, especially from 0.0001 to 0.01 mol %, based on equivalents of dicarboxylic acid. The reaction of adipic acid with acetylene is particularly preferred.
A further preferred embodiment relates to the reaction of the compounds of the formula II in which R¹is phenyl which may be substituted as defined under c) above, and n is 2, 3, 4, 5 or 6, especially 2 or 3, with acetylene. Preference is given to carrying out this reaction at a temperature in the range from 140 to 230° C., in particular from 150 to 200° C. The catalyst is used preferably in an amount of from 0.00001 to 0.1 mol %, especially from 0.0001 to 0.01 mol %, based on equivalents of polycarboxylic acid.
The present invention also provides compounds of the formula I
in which R¹is aryl and n is 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy, amino, mono-C₁-C₄-alkylamino, di-C₁-C₄-alkylamino, —OCOR³, —COOR³, —CONR⁴R⁵, —NR⁴COR⁵, —OCONR⁴R⁵or —NR⁴COOR⁵or R¹is C₃-C₇-cycloalkyl and n is 2 or 3, and R²is H, C₁-C₈-alkyl, phenyl-C₁-C₄-alkyl, phenyl which is optionally substituted by 1 or 2 C₁-C₄-alkyl groups, or C₃-C₇-cycloalkyl.
Particular preference is given to the preparation of divinyl phthalate, divinyl terephthalate and divinyl isophthalate, and also of divinyl cyclohexane-1,2, divinyl cyclohexane-1,3 and divinyl cyclohexane-1,4, vinyl pyridine-2-carboxylate, vinyl pyridine-3-carboxylate and vinyl pyridine-4-carboxylate, and also vinyl nicotinate.
The present invention also provides the compounds of the formula I in which R¹is bicycloalkyl having from 6 to 9 carbon atoms or bicycloalkenyl having from 6 to 9 carbon atoms and one or two carbon-carbon double bonds and n is 1 or 2, or in which R¹is five- or six-membered heteroalkyl which has one or two heteroatoms which are each independently selected from N, O and S, where n is 1, 2 or 3; and R²is H, C₁-C₈-alkyl, phenyl-C₁-C₄-alkyl, phenyl which is optionally substituted by 1 or 2 C₁-C₄-alkyl groups, or C₃-C₇-cycloalkyl.
The vinyl esters obtainable by the process according to the invention are suitable for use in materials which can be cured thermally or by energy-rich radiation. The materials may be used as or in coating compositions, for example lacquers, printing inks or adhesives, as printing plates, as moldings, for producing photoresists, in stereolithography or as a casting material, for example for optical lenses. Substrates for the coating may, for example, be textile, leather, metal, plastic, glass, wood, paper or paperboard. The compounds of the formula I are usable as crosslinking agents in free-radical and cationic polymerizations. They are preferably used in UV-curable coatings, for example as reactive diluents.
The examples which follow illustrate the invention without restricting it. The GC analyses (GC: gas chromatography) were effected on a capillary column with a Carbowax (polyethylene glycol) film, for example DB Wax from J & W Scientific.

EXAMPLES

Example 1

A mixture of 36.0 g of benzoic acid (295 mmol), 0.25 g of Re₂(CO)₁₀(0.38 mmol) and 78.0 g of toluene were subjected to vinylation at 140° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. The yield determined by GC analysis was 99%.

Example 2

A mixture of 8.0 g of adipic acid (55 mmol), 0.10 g of Re(CO)₅Cl (0.28 mmol) and 17.3 g of toluene was subjected to vinylation at 140° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. The yield determined by GC analysis was 96%.

Example 3

A mixture of 8.0 g of adipic acid (55 mmol), 0.10 g of Re(CO)₅Br (0.25 mmol) and 17.3 g of toluene was subjected to vinylation at 140° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. The yield determined by GC analysis was 95%.

Example 4

A mixture of 36.0 g of adipic acid (247 mmol), 0.10 g of Re₂(CO)₁₀(0.15 mmol) and 78.0 g of toluene were subjected to vinylation at 140° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. The yield determined by GC analysis was 98%.

Example 5

A mixture of 300.0 g of adipic acid (2.045 mol), 1.00 g of Re₂(CO)₁₀(1.50 mmol) and 700.0 g of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. The distillative workup of the reaction mixture in the presence of a polymerization inhibitor afforded the divinyl ester of the carboxylic acid in a yield of 87%.

Example 6

A mixture of 100.0 g of adipic acid (681.6 mol) and 0.50 of Re₂(CO)₁₀(0.75 mmol) was heated to 200° C. without solvent for 2 h. After cooling to 160° C., the mixture was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h to obtain divinyl adipate.

Example 7

A mixture of 8.0 g of terephthalic acid (48 mmol), 0.10 g of Re₂(CO)₁₀(0.15 mmol) and 17.3 g of toluene was subjected to vinylation at 140° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Divinyl terephthalate was obtained, which was detectable by means of GC-MS analysis.

Example 8

A mixture of 30.0 g (259 mmol) of fumaric acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 8 h. Divinyl fumarate was detected as the main product by means of GC-MS and GC analysis.

Example 9

A mixture of 30.0 g (181 mmol) of phthalic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 12 h. Divinyl phthalate was detected as the main product by means of GC-MS and GC analysis.

Example 10

A mixture of 30.0 g (181 mmol) of isophthalic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 20 h. Divinyl isophthalate was detected as the main product by means of GC-MS and GC analysis.

Example 11

A mixture of 30.0 g (197 mmol) of 4-methoxybenzoic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 18 h. Vinyl 4-methoxybenzoate was detected as the main product by means of GC-MS and GC analysis.

Example 12

A mixture of 30.0 g (326 mmol) of pivalic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 7 h. Vinyl pivalate was detected as the main product by means of GC-MS and GC analysis.

Example 13

A mixture of 30.0 g (348 mmol) of crotonic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Vinyl crotonate was detected as the main product by means of GC-MS and GC analysis.

Example 14

A mixture of 30.0 g (184 mmol) of 4-dimethylaminobenzoic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Vinyl 4-dimethylamino-benzoate was detected as the main product by means of GC-MS and GC analysis.

Example 15

A mixture of 30.0 g (192 mmol) of 4-chlorobenzoic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 20 h. Vinyl 4-chlorobenzoate was detected as the main product by means of GC-MS and GC analysis.

Example 16

A mixture of 30.0 g (417 mmol) of acrylic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 140° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 17 h. Vinyl acrylate was detected as the main product by means of GC-MS and GC analysis.

Example 17

A mixture of 30.0 g (149 mmol) of 4-bromobenzoic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 4 h. Vinyl 4-bromobenzoate was detected as the main product by means of GC-MS and GC analysis.

Example 18

A mixture of 30.0 g (348 mmol) of methacrylic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 140° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 13 h. Vinyl methacrylate was detected as the main product by means of GC-MS and GC analysis.

Example 19

A mixture of 40.0 g (241 mmol) of terephthalic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 175° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 2 h. Divinyl terephthalate was detected as the main product by means of GC-MS and GC analysis.

Example 20

A mixture of 40.0 g (345 mmol) of hexanoic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 1 h. Vinyl hexanoate was detected as the main product by means of GC-MS and GC analysis.

Example 21

A mixture of 40.0 g (313 mmol) of cyclohexanoic acid, 0.5 g of Re₂(CO)₁₀(0.77 mmol) and 90 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 3.5 h. Vinyl cyclohexanoate was detected as the main product by means of GC-MS and GC analysis.

Example 22

A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re₂(CO)₁₀(0.12 mmol) and 100 ml of xylene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 24 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 23

A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re₂(CO)₁₀(0.12 mmol) and 100 ml of dioxane was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 2 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 24

A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re₂(CO)₁₀(0.12 mmol) and 100 ml of THF was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 1 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 25

A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re₂(CO)₁₀(0.12 mmol) and 100 ml of NMP was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 2.5 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 26

A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re₂(CO)₁₀(0.12 mmol) and 100 ml of diphenyl ether was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 2 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 27

A mixture of 6.5 g (253 mmol) of adipic acid, 0.08 g of Re₂(CO)₁₀(0.12 mmol) and 100 ml of decalin was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 10 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 28

A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re₂(CO)₁₀(0.12 mmol) and 100 ml of paraffin oil was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 12 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 29

A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re₂(CO)₁₀(0.12 mmol) and 100 ml of acetonitrile was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 12 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 30

A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re₂(CO)₁₀(0.12 mmol) and 100 ml of butyrolactone was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 26 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 31

A mixture of 36.5 g (253 mmol) of adipic acid, 0.08 g of Re₂(CO)₁₀(0.12 mmol) and 100 ml of divinyl adipate was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 24 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 32

A mixture of 36.5 g (253 mmol) of adipic acid, 0.05 g of Re₂O₇(1.03 mmol) and 90 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 33

A mixture of 8.0 g (56 mmol) of adipic acid, 0.10 g of rhenium powder (0.54 mmol) and 20 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Divinyl adipate was detected by means of GC analysis.

Example 34

A mixture of 36.5 g (253 mmol) of adipic acid, 0.073 g of ReCl₃(0.25 mmol) and 100 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 30 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 35

A mixture of 36.5 g (253 mmol) of adipic acid, 0.062 g of ReCH₃O₃(0.25 mmol) and 100 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 30 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 36

A mixture of 36.5 g (253 mmol) of adipic acid, 5.0 g of Re₂O₇on SiO₂/Al₂O₃(3% Re, 0.8 mmol) and 100 ml of toluene was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 5 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 37

A mixture of 18.25 g (127 mmol) of adipic acid, 0.021 g of Re₂(CO)₁₀(0.03 mmol) and 60 ml of divinyl adipate was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 7 bar for 9.5 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 38

A mixture of 18.25 g (127 mmol) of adipic acid, 0.021 g of Re₂(CO)₁₀(0.03 mmol) and 60 ml of divinyl adipate was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 4 bar for 8 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 39

A mixture of 18.25 g (127 mmol) of adipic acid, 0.021 g of Re₂(CO)₁₀(0.03 mmol) and 60 ml of divinyl adipate was subjected to vinylation at 160° C., a nitrogen pressure of 1 bar and an acetylene pressure of 3 bar for 11 h. Divinyl adipate was detected as the main product by means of GC-MS and GC analysis.

Example 40

A mixture of 40.0 g (181 mmol) of cyclohexane-1,4-dicarboxylic acid, 0.05 g of Re₂(CO)₁₀(0.08 mmol) and 90 ml of dioxane was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 5 h. Divinyl cyclohexane-1,4-dicarboxylate was detected as the main product by means of GC-MS and GC analysis.

Example 41

A mixture of 8.0 g (55 mmol) of adipic acid, 1.33 g of Mn₂(CO)₁₀(3.4 mmol) and 20 ml of dioxane was subjected to vinylation at 140° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6 h. Divinyl adipate was detected by means of GC analysis.

Example 42

A mixture of 12.0 g (82 mmol) of adipic acid, 2.00 g of Mo(CO)₆(7.6 mmol) and 30 ml of toluene was subjected to vinylation at 150° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6.5 h. Divinyl adipate was detected by means of GC analysis.

Example 43

A mixture of 8.0 g (55 mmol) of adipic acid, 1.33 g of Fe(CO)₅(6.8 mmol) and 20 ml of toluene was subjected to vinylation at 140° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6.0 h. Divinyl adipate was detected by means of GC analysis.

Example 44

A mixture of 40.0 g (171 mmol) of butanetetracarboxylic acid, 50 mg of Re₂(CO)₁₀(0.08 mmol) and 80 g of xylene (isomer mixture) was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 14.0 h. Tetravinyl butanetetracarboxylate was detected by means of MS analysis.

Example 45

A mixture of 10.0 g (55 mmol) of norbornenedicarboxylic acid, 50 mg of Re₂(CO)₁₀(0.08 mmol) and 80 g of xylene (isomer mixture) was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 4.0 h. Divinyl norbornenate was detected by means of GC analysis.

Example 46

A mixture of 15.0 g (46 mmol) of 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid (Het acid), 50 mg of Re₂(CO)₁₀(0.08 mmol) and 15 g of xylene (isomer mixture) was subjected to vinylation at 160° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 6.0 h. Het acid divinyl ester was detected by means of GC-MS analysis.

Example 47

A mixture of 45.0 g (308 mmol) of adipic acid, 100 mg of Re₂(CO)₁₀(0.153 mmol) and 105 g of xylene (isomer mixture) was subjected to vinylation at 200° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 9 h. Divinyl adipate was detected as the main product by means of GC analysis.

Example 48

A mixture of 7.5 g (51 mmol) of adipic acid, of 100 mg of Re₂(CO)₁₀(0.153 mmol) and 142.5 g of xylene (isomer mixture) was subjected to vinylation at 240° C., a nitrogen pressure of 2 bar and an acetylene pressure of 18 bar for 9 h. Divinyl adipate was detected as the main product by means of GC analysis.

Claims

1. A process for preparing vinyl carboxylate compounds of the formula I:

in which

a) R¹is H or —COO—CH═CH—R²and n is 1,

b) R¹is C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl or C₃-C₇-cycloalkyl, and n is 1, 2, 3 or 4, where R¹is optionally substituted by 1, 2 or 3 radicals which are each independently selected from phenyl, halogen, hydroxy, C₁-C₄-alkoxy, amino, mono-C₁-C₄-alkylamino, di-C₁-C₄-alkylamino, —OCOR³, —COOR³, —CONR⁴R⁵, —NR⁴COR⁵, —OCONR⁴R⁵or —NR⁴COOR⁵, or

c) R¹is aryl and n is 1, 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from C₁-C₄-alkyl, halogen, hydroxy, C₁-C₄-alkoxy, amino, mono-C₁-C₄-alkylamino, di-C₁-C₄-alkylamino, —OCOR³, —COOR³, —CONR⁴R⁵, —NR⁴COR⁵, —OCONR⁴R⁵or —NR⁴COOR⁵, or

d) R¹is bicycloalkyl having from 7 to 9 carbon atoms or bicycloalkenyl having from 7 to 9 carbon atoms and one or two carbon-carbon double bonds, and n is 1 or 2, where the bicycloalkyl radical may be substituted by 1, 2, 3, 4, 5 or 6 radicals which are each independently selected from halogen or C₁-C₄-alkyl, or

e) R¹is five- or six-membered heterocyclyl which has one or two heteroatoms which are each independently selected from N, O and S, and n is 1, 2 or 3, where the heterocyclyl radical may be substituted by 1 or 2 radicals which are each independently selected from halogen or C₁-C₄-alkyl;

R²is H, C₁-C₈-alkyl, phenyl-C₁-C₄-alkyl, phenyl which is optionally substituted by 1 or 2 C₁-C₄-alkyl groups, or C₃-C₇-cycloalkyl;

R³is C₁-C₄-alkyl; and

R⁴and R⁵, which may be the same or different, are each H or C₁-C₄-alkyl;

the process comprising the reaction of a compound of the formula II

in which R¹is H, —COOH or as defined in b) or c) and n is as defined in d)

with a compound of the formula III

H—C≡C—R² (III)

in which R²is as defined above, in the presence of a catalyst which is at least one selected from the group consisting of carbonyl complexes, oxides and halides of rhenium, of manganese, of tungsten, of molybdenum, of chromium and of iron, and a rhenium metal at a temperature of ≦300° C.

2. The process according to claim 1, wherein the catalyst is at least one selected from the group consisting of carbonyl complexes, and oxides and halides of rhenium, of manganese and of molybdenum.

3. The process according to claim 2, wherein the catalyst used is Re₂(CO)₁₀.

4. The process according to claim 1, wherein the catalyst is used in an amount of from 0.000005 to 1 mol % based on equivalents of the compound of the formula II.

5. The process according to claim 1, wherein the compound of the formula III is selected from the group consisting of acetylene, propyne, 1-butyne, 1-pentyne, 1-hexyne and phenylacetylene.

6. The process according to claim 1, wherein the compound of the formula II used is an aliphatic monocarboxylic acid.

7. The process according to claim 6, wherein the aliphatic monocarboxylic acid is at least one selected from the group consisting of acetic acid, phenylacetic acid, propionic acid, alanine, butyric acid, hydroxybutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-methylpropionic acid, 2-methylbutyric acid, 3-methylbutyric acid, 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, pivalic acid, 2,2-dimethylbutyric acid, 2,2-dimethylpentanoic acid, 2,2-dimethylhexanoic acid, 2,2-dimethylheptanoic acid, 2,2-dimethyloctanoic acid, neononanoic acid, neodecanoic acid, neotridecanoic acid, stearic acid, oleic acid, lauric acid, palmitic acid, cyclohexanecarboxylic acid, acrylic acid, methacrylic acid, crotonic acid and cinnamic acid.

8. The process according to claim 1, wherein the compound of the formula II is an aliphatic polycarboxylic acid.

9. The process according to claim 8, wherein the aliphatic polycarboxylic acid is at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, agaric acid, 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, citric acid, malic acid, tartaric acid, glutamic acid, maleic acid and fumaric acid.

10. The process according to claim 9, wherein the compound of the formula II is adipic acid.

11. The process according to claim 1, wherein the compound of the formula II is a cycloaliphatic mono- or dicarboxylic acid.

12. The process according to claim 11, wherein the compound of the formula II is cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid or cyclohexane-1,4-dicarboxylic acid.

13. The process according to claim 1, wherein the compound of the formula II is a bicyclic or heterocyclic mono- or dicarboxylic acid.

14. The process according to claim 13, wherein the compound of the formula II is selected from the group consisting of

15. The process according to claim 13, wherein the compound of the formula II is at least one selected from the group consisting of 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, furan-2-carboxylic acid, furan-3-carboxylic acid, thiophene-2-carboxylic acid, thiophene-3-carboxylic acid and proline.

16. The process according claim 8, wherein the reaction is carried out at a temperature in the range from 70 to 260° C.

17. The process according claim 8, wherein the catalyst is used in an amount of from 0.000001 to 0.0025 mol %, based on equivalents of the compound of the formula II.

18. The process according 1, wherein the compound of the formula II is an aromatic monocarboxylic acid or an aromatic polycarboxylic acid.

19. The process according to claim 18, wherein the compound of the formula II is at least one selected from the group consisting of benzoic acid, 2-, 3- or 4-methylbenzoic acid, salicylic acid, 2-, 3- or 4-aminobenzoic acid, 4-dimethylaminobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid, benzenepentacarboxylic acid and benzenehexacarboxylic acid.

20. The process according to claim 18, wherein the reaction is carried out at a temperature in the range from 140 to 230° C.

21. The process according to claim 1, where the compound of the formula III is used in an excess of from 0.1 to 20 mol %, based on equivalents of the compound of the formula II.

22. The process according to claim 1, wherein the compound of the formula III is acetylene.

23. A vinyl carboxylate of the formula I

in which R¹is aryl and n is 2, 3, 4, 5 or 6, where aryl is optionally substituted by 1, 2 or 3 radicals which are each independently selected from the group consisting of C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy, amino, mono-C₁-C₄-alkylamino, di-C₁-C₄-alkylamino, —OCOR³, —COOR³, —CONR⁴R⁵, —NR⁴COR⁵, —OCONR⁴R⁵and —NR⁴COOR⁵, or in which R¹is C₃-C₇-cycloalkyl and n is 2 or 3; and R²is H, C₁-C₈-alkyl, phenyl-C₁-C₄-alkyl, phenyl which is optionally substituted by 1 or 2 C₁-C₄-alkyl groups, or C₃-C₇-cycloalkyl.

24. The vinyl carboxylate according to claim 22 of the formula I in which R²is H.

25. The vinyl carboxylate according to claim 24, which is at least one selected from the group consisting of divinyl cyclohexane-1,2-dicarboxylate, divinyl cyclohexane-1,3-dicarboxylate and divinyl cyclohexane-1,4-dicarboxylate.

26. The vinyl carboxylate according to claim 25, which is divinyl cyclohexane-1,4-dicarboxylate.

27. A tetravinyl butane-1,2,3,4-tetracarboxylate compound.

28. The vinyl carboxylate of the formula I:

in which R¹is bicycloalkyl having from 6 to 9 carbon atoms or bicycloalkenyl having from 6 to 9 carbon atoms and one or two carbon-carbon double bonds and n is 1 or 2, or in which R¹is five- or six-membered heterocyclyl which has one or two heteroatoms which are each independently selected from N, O and S, where n is 1, 2 or 3; and R²is H, C₁-C₈-alkyl, phenyl-C₁-C₄-alkyl, phenyl which is optionally substituted by 1 or 2 C₁-C₄-alkyl groups, or C₃-C₇-cycloalkyl.

29. A process for making crosslinkers or reactive diluents comprising adding the vinyl carboxylates according to claim 23 to a composition.